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CN114927258B - Environment-friendly antioxidant conductive copper paste and preparation method and application thereof - Google Patents

Environment-friendly antioxidant conductive copper paste and preparation method and application thereof Download PDF

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Publication number
CN114927258B
CN114927258B CN202210646875.3A CN202210646875A CN114927258B CN 114927258 B CN114927258 B CN 114927258B CN 202210646875 A CN202210646875 A CN 202210646875A CN 114927258 B CN114927258 B CN 114927258B
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environment
copper powder
copper paste
friendly
conductive copper
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CN114927258A (en
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颜志勇
胡英
万禛
王晓馨
于利超
易洪雷
张葵花
姚勇波
李喆
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Jiaxing University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Conductive Materials (AREA)

Abstract

The invention relates to an environment-friendly antioxidant conductive copper paste and a preparation method thereof, wherein the conductive copper paste comprises the following raw materials in percentage by mass: 40-70wt.% of copper powder, 0.1-5wt.% of organic binder, 3-10wt.% of biological reducing agent, 10-50wt.% of solvent and 0.1-6wt.% of other additives. The obtained environment-friendly antioxidant conductive copper paste can realize low-temperature curing at 180-200 ℃, and after the copper paste product is stored for 45 days in room temperature air atmosphere, the volume resistivity of the sintered copper wire or copper film is still less than 5 multiplied by 10 ‑5 Omega cm, the conductivity of the alloy is still comparable with that of copper paste on the market. The environment-friendly antioxidant conductive copper paste prepared by the invention is suitable for circuit printing in flexible devices or electronic element preparation, and the used raw materials are environment-friendly, pollution-free and nontoxic, and meet the environment-friendly production requirement.

Description

Environment-friendly antioxidant conductive copper paste and preparation method and application thereof
Technical Field
The invention belongs to the field of material science, relates to a preparation method of conductive paste, and in particular relates to environment-friendly antioxidant conductive copper paste and a preparation method thereof.
Background
The conductive paste is widely applied to the fields of metallurgy, chemical industry, electronic technology and the like as an important functional material, and generally mainly comprises three parts: a conductive phase, a binder phase, and an organic carrier. The conductive phase, which is typically a metal particulate, an alloy particulate, and mixtures thereof, determines the basic properties of the conductive paste and affects the physical and mechanical properties of the paste product. The binder phase is used to bond the conductive paste film layer to the substrate material firmly, and is usually an organic binder or an inorganic binder, such as epoxy resin or a mixture of glass frit and oxide crystals, etc., and affects the mechanical properties and dielectric properties of the film. The organic carrier is a mixture of organic polymer, surfactant, dispersant, thixotropic agent and the like and solvent, and is a carrier of conductive phase and binding phase, and is used for wetting and dispersing conductive phase particles and regulating rheological property of conductive paste.
The conductive paste is usually made of noble metal silver, gold and the like, and has excellent conductivity and oxidation resistance, but the noble metal is low in stock and high in cost, and the metal silver particles are easy to generate electron migration effect in the use process, so that the reliability of the product is poor. The metal copper is an ideal substitute material for preparing the conductive paste, the copper reserves in China are rich, the price is much cheaper than silver and gold materials, and the conductivity is only inferior to silver. However, copper has very active chemical properties, and is easy to oxidize when exposed to air at normal temperature, so that an oxide film layer is formed on the surface of the copper, the resistivity of the oxide film layer is high, the conductivity is reduced, the practicability of the copper is greatly reduced, and the oxide film layer can greatly improve the heat treatment temperature of the conductive paste and increase the processing difficulty.
In the prior art, in order to prevent oxidation of copper powder, the method adopted generally comprises the following steps: (1) Silver or nickel is plated on the surface of copper powder, silver or nickel is not easily oxidized in air, the copper is protected, but the uniformity and coverage rate of a plating layer on the surface of copper powder after silver plating or nickel plating cannot be well ensured; (2) Adding antioxidant components into the organic carrier, such as an antioxidant or deoxidizer, wherein the antioxidant or deoxidizer is oxidized before copper powder contacts oxygen, so that the contact probability of oxygen and copper powder is reduced, hydrazine hydrate as an antioxidant is toxic, and the deoxidizer such as phosphorus-containing organic matters, rare earth elements and the like, but adding phosphorus severely reduces the conductivity of copper, so that the copper loses the function of serving as an electronic material, and the problem of environmental pollution exists when adding the rare earth elements; (3) The copper powder is coated by the organic high molecular polymer, a protective shell layer is formed on the surface of the copper powder to isolate oxygen, but the shell layer structure is easy to break in the production and processing process, the risk of oxidization still exists when the shell layer structure is exposed in the air, the required amount of the surface coating agent is more than several times of the volume of the copper, the large volume shrinkage during sintering can be caused, a high-density sintered body is difficult to obtain, and the conductivity is further deteriorated; (4) The adoption of a reducing sintering atmosphere, such as hydrogen, is flammable and explosive, and the problem of how to effectively avoid gas leakage technically remains to be solved; (5) The organic corrosion inhibitor is added to form a protective coating on the surface of the copper powder, and the protective coating can be used as a representative corrosion inhibitor such as imidazole compound, so that the oxidation of the copper powder can be effectively prevented, but the heat resistance is poor, when the heat treatment step is performed at the temperature exceeding 150 ℃, serious heat history can occur, the formation of a surface oxide film with poor conductivity of the copper powder is promoted, and the conductivity is greatly reduced; (6) The method can effectively solve the problem of copper powder oxidation by inhibiting copper powder oxidation through low-temperature sintering.
The application of high-temperature sintering on a resin substrate is known to be difficult, for example, patent CN200810142382.6 is to weigh three mixed copper powder, glass powder and an organic carrier with different granularities in proportion, and copper slurry is prepared by mixing, grinding and dispersion rolling.
At present, low-temperature sintering copper paste is reported, for example, patent CN201710534066.2 reports an electronic paste based on low-melting-point metal micro-nano powder and a preparation method thereof, and low-melting-point metal or alloy (melting point is-78-232 ℃) is adopted as a conductive phase to reduce the sintering temperature, but metals such as chromium, mercury and the like are not environment-friendly and easily cause environmental pollution; the patent CN202110392854.9 adopts copper paste with the granularity of 1-20 mu m to realize low-temperature curing at 180-300 ℃, but the reagents such as phenyl glycidyl ether, cyclohexanone and the like have toxic action on the environment or human body, and are not environment-friendly; patent CN201910315885.7 reports a low-temperature conductive copper paste and a preparation method thereof, wherein silver-coated copper powder with the powder particle diameter of 5-15 mu m is adopted, the curing temperature is high, the temperature cannot reach below 200 ℃, in addition, the surface of the silver-coated copper powder is often cracked, finally, the oxidation of a copper core is still caused, and the cost of the conductive paste is increased due to the use of silver and a copper plating process; the patent CN201910727885.8 is characterized in that low-melting-point SnAgCu alloy powder with the melting point of 218 ℃ is added into micron copper powder, the SnAgCu alloy powder is melted and forms intermetallic compounds with the micron copper powder, and the intermetallic compounds can be sintered and solidified at a low temperature of 180-250 ℃, but the alloy powder contains metal silver, so that the cost is increased, and the used reducing agent sodium phosphate is not environment-friendly and has pollution risk.
In summary, the oxidation problem and the low-temperature heat treatment problem of copper powder limit the application of copper powder in the field of conductive paste to a great extent, so that it is necessary to develop an anti-oxidation conductive copper paste which is environment-friendly and can be sintered at 180-200 ℃ so that the anti-oxidation conductive copper paste can be applied to various substrate materials and the application range of the anti-oxidation conductive copper paste is widened.
Disclosure of Invention
In order to solve the technical problems in the prior art, one of the purposes of the invention is to provide an environment-friendly oxidation-resistant conductive copper paste which can be sintered and solidified at a low temperature of 180-200 ℃ and has excellent oxidation resistance and conductivity, and the volume resistivity of a copper wire or a copper film after sintering is still less than 5 multiplied by 10 after the environment-friendly oxidation-resistant conductive copper paste product is stored for 45 days in an air atmosphere at room temperature -5 Omega cm, the conductivity is better than most copper conductive pastes on the market.
The environment-friendly antioxidant conductive copper paste comprises the following raw materials: 40-70wt.% of copper powder, 0.1-5wt.% of organic binder, 3-10wt.% of biological reducing agent, 0.1-6wt.% of other additives and 10-50wt.% of solvent, wherein the addition ratio of the raw material components is 100%.
According to an embodiment of the invention, the bioreductive agent is capsaicin or a combination of capsaicin and one or more of chitin, resveratrol, tannic acid, chlorogenic acid, caffeic acid, piperine;
preferably, the bioreductive agent is capsaicin, capsaicin: chitin=1:1 (mass ratio), capsaicin: resveratrol=1:1 (mass ratio), capsaicin: chlorogenic acid=1:1 (mass ratio), capsaicin: caffeic acid=1:1 (mass ratio);
furthermore, the capsaicin is trans-8-methyl-N-vanillyl-6-nonenamide, is colorless and odorless crystal powder, has hydroxyl, methoxy, alkenyl and amido in the molecular structure, has adsorption interaction with copper powder, has hetero atoms and pi bonds in the capsaicin capable of transferring electrons to the surface of the copper powder, inhibits oxidation of the copper powder, plays a role in corrosion inhibition, has large steric hindrance of the molecular structure of the capsaicin, can protect and stabilize the copper powder, and also has a certain dispersion effect on the copper powder;
furthermore, the chitin, resveratrol, tannic acid, chlorogenic acid, caffeic acid and piperine all contain N, O heteroatoms and all contain unsaturated bonds, hydroxyl groups and other structures, so that electrons can be given out to play a role in reduction, and the prepared environment-friendly antioxidant conductive copper paste has oxidation resistance.
Preferably, the other additives include defoamers, thixotropic agents and dispersants; wherein,,
the defoaming agent is a polyether type defoaming agent or an organosilicon defoaming agent, the polyether type defoaming agent comprises a polyether defoaming agent GP-330, a polyether defoaming agent GPE-3000 or a polyether defoaming agent PPG-1000, and the organosilicon defoaming agent comprises an organosilicon defoaming agent FAG-470, an organosilicon defoaming agent BYK-065, an organosilicon defoaming agent BYK-066N or a polysiloxane defoaming agent YCK-615; the addition amount of the defoaming agent accounts for 0.1-2 wt% of the environment-friendly antioxidant conductive copper paste, and the defoaming agent has the functions of reducing bubbles in the process of mixing and stirring the paste, reducing pores in the process of sintering the environment-friendly copper conductive paste, enabling the sintering to be compact and reducing the resistance;
the thixotropic agent is hydrogenated castor oil, oxidized polyethylene wax, polyamide wax, palmitol, span-85 or ethylene glycol, and the addition amount of the thixotropic agent accounts for 0.1-3wt.% of the environment-friendly antioxidant conductive copper paste; the thixotropic agent has the function of enabling the slurry to obtain necessary thixotropic property, has fluidity when being subjected to the action of shearing force, and restores the original state of the slurry when not being subjected to the action of shearing force; excessive addition of the thixotropic agent can cause difficult removal of the environment-friendly copper conductive paste in the sintering and curing process, and the thixotropic property of the environment-friendly copper conductive paste cannot be effectively provided if the addition is too small.
The dispersing agent is amino clay or attapulgite clay, wherein the amino clay is phyllosilicate, and the adding amount of the dispersing agent accounts for 0.1-1 wt% of the environment-friendly antioxidant conductive copper paste;
wherein, the amino clay is a self-made product, and the specific preparation method comprises the following steps: dissolving magnesium chloride hexahydrate in 200mL of absolute ethyl alcohol, fully stirring for 30min, dropwise adding gamma-aminopropyl triethoxysilane, continuously stirring until the reaction is complete, centrifuging the obtained white suspension at 5000rpm for 5min, drying at 45 ℃ for 24h in a vacuum drying oven, grinding into powder, and placing into a dryer for later use, wherein the gamma-aminopropyl triethoxysilane: the mass ratio of the magnesium chloride hexahydrate is 1.25-1.35, and the required amino clay can be prepared within the range of the mass ratio; the structure of the amino clay is a layered structure, so that oxygen in the air can be shielded, and the amino groups on the surface of the amino clay show reducibility, so that the oxidation resistance of copper in the copper slurry can be improved;
the attapulgite is a commercial product, preferably 1200-mesh attapulgite sold by Ming-Guang-Chemicals mineral Co-Ltd, and has grey-white internal multi-pore canal, so that the structure can reduce heat emission of the environment-friendly copper conductive paste during sintering, reduce sintering solidification temperature, and the surface of the attapulgite also contains hydroxyl groups, so that a certain antioxidation effect can be achieved during the sintering process; the amino clay or the attapulgite not only has a dispersing effect due to the structural characteristics, but also has the effect of adjusting the viscosity of the environment-friendly copper conductive paste.
The copper powder comprises: one or two of spherical copper powder, flake copper powder, dendritic copper powder, rod copper powder, fibrous copper powder or polyhedral copper powder,
wherein, the average grain diameter of the spherical copper powder is 0.05-0.5 mu m, the average grain diameter of the flake copper powder is 2-10 mu m, the average thickness is 0.05-0.2 mu m, the average grain diameter of the dendritic copper powder is 3-5 mu m, the average diameter of the rod copper powder is 0.05-0.1 mu m, the average length is 1-2.5 mu m, the average diameter of the fibrous copper powder is 0.03-0.05 mu m, the average length is 10-30 mu m, and the average grain diameter of the polyhedral copper powder is 0.1-2 mu m;
preferably, the copper powder can be spherical copper powder and flaky copper powder according to the mass ratio of 1:0.1-0.5, spherical copper powder and dendritic copper powder according to the mass ratio of 1:0.1-0.5, spherical copper powder and rod-shaped copper powder according to the mass ratio of 1:0.1-0.5, spherical copper powder and fibrous copper powder according to the mass ratio of 1:0.1-0.5, polyhedral copper powder and dendritic copper powder according to the mass ratio of 1:0.1-0.5; the copper powder compounding with different shapes can promote the effective contact and connection between copper powder, and can ensure the conductivity of the environment-friendly antioxidant conductive copper paste after sintering on the basis of reducing the copper powder consumption.
Preferably, the organic binder is polyvinyl alcohol resin (molecular weight of 5000-10000), polyvinylpyrrolidone K-30 (molecular weight of 44000-54000), polyethylene glycol-400, acrylic resin (molecular weight of 5000-10000), hydroxyethyl cellulose, hydroxypropyl cellulose, gelatin, shellac or gum arabic; the selected organic binder can enhance the decomposability of the environment-friendly oxidation-resistant conductive copper paste during sintering, and a compact conductor path with low resistance is obtained.
Preferably, the solvent is one or more of terpineol, carbitol, butyl carbitol, diethylene glycol ether acetate, dibutyl phthalate, tributyl citrate, ethylene glycol, propylene glycol, aminomethylpropanol, diethylene glycol, triethylene glycol, diglyme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, monoethanolamine, diethanolamine, triethanolamine.
The invention also aims to provide a preparation method of the environment-friendly antioxidant conductive copper paste, which comprises the following steps:
(1) Dissolving an organic binder in a solvent, adding a defoaming agent, a thixotropic agent and a dispersing agent, heating in a water bath at 30-60 ℃, stirring until the organic binder is completely dissolved, and sieving to remove impurities to obtain an organic carrier;
(2) Uniformly dispersing copper powder, a biological reducing agent and the solvent by ultrasonic, mixing with the organic carrier and dispersing to obtain uniform first slurry; and (3) fully stirring and dispersing the first slurry in a high-speed mixer or a planetary stirrer for 10-30min, then performing rolling and dispersing in a three-roller mill for 3-5 times, wherein the rolling speed is 400-500rpm, the rolling time is 2-5h, the rolling fineness is ensured to be less than 1 mu m, a second slurry is obtained, and finally the second slurry is filtered by a filter screen of 5-10 mu m, so that the environment-friendly antioxidant conductive copper slurry is obtained.
Wherein, the screening in the step (1) adopts a 300-mesh stainless steel net or a polyester net to filter and remove impurities, thereby ensuring the uniformity and fineness of the slurry.
The organic carrier in the step (1) comprises the following components in percentage by mass: organic binder: solvent: defoaming agent: thixotropic agent: dispersant = 0.1-8:10-50:0.1-2:0.1-3:0.1-1.
In the step (2), the viscosity of the first slurry is controlled within the range of 15pa·s-65pa·s, if the viscosity is too large, the copper slurry is not easy to be uniformly mixed and has poor fluidity, which will adversely affect the operations such as spreading and filling of the environment-friendly antioxidant conductive copper slurry, if the viscosity is too small, the shrinkage failure of the environment-friendly antioxidant conductive copper slurry during drying will be disadvantageously increased, a dense conductive path cannot be formed, the resistance is increased, and the conductivity is reduced.
In addition, the invention also claims the application of the environment-friendly oxidation-resistant conductive copper paste in flexible devices.
In particular to application of the environment-friendly oxidation-resistant conductive copper paste in circuit printing or electronic element preparation in flexible devices.
Furthermore, the environment-friendly antioxidant conductive copper paste prepared by the invention is suitable for circuit printing in flexible devices or electronic element preparation, and the used raw materials are environment-friendly, pollution-free and nontoxic, and meet the environment-friendly production requirement.
Based on the above, the environment-friendly antioxidant conductive copper paste provided by the invention and the preparation method and application thereof have the following advantages compared with the prior art:
(1) The environment-friendly antioxidant conductive copper paste prepared by the invention can be sintered and solidified at a low temperature of 180-200 ℃, has excellent oxidation resistance and conductivity, and the volume resistivity of a copper wire or copper film after sintering is still less than 5 multiplied by 10 after the environment-friendly antioxidant conductive copper paste product is stored for 45 days in an air atmosphere at room temperature -5 Omega cm, the conductivity is better than most copper conductive paste on the market;
(2) The biological reducing agent is selected, hetero atoms (N, O) and pi bonds in the biological reducing agent can transfer electrons to the surface of copper powder, inhibit oxidation of the copper powder, play a role in corrosion inhibition, have large steric hindrance of capsaicin molecular structure, can protect and stabilize the copper powder, and play a role in dispersion; the raw materials are environment-friendly and pollution-free.
(3) According to the invention, the anti-oxidation sintering of the environment-friendly anti-oxidation conductive copper paste can be realized under the protection of nitrogen atmosphere by self-making the organic carrier, so that the process for preparing the environment-friendly anti-oxidation conductive copper paste is simple, and the biological antioxidant is environment-friendly and economical.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an environment-friendly oxidation-resistant conductive copper paste, which comprises the following raw materials in percentage by mass: 40-70wt.% of copper powder, 0.1-5wt.% of organic binder, 3-10wt.% of biological reducing agent, 0.1-6wt.% of other additives and 10-50wt.% of solvent, wherein the addition ratio of the raw material components is 100%.
And printing the prepared environment-friendly antioxidant conductive copper paste on an alumina ceramic substrate by a screen printing technology, then placing the ceramic substrate in a muffle furnace at 180 ℃ for sintering and curing, and testing the resistivity of the obtained sample by using a four-probe tester.
The invention is further illustrated, but is not limited, by the following examples.
Example 1
The preparation method of the environment-friendly antioxidant conductive copper paste specifically comprises the following steps:
(1) Dissolving polyvinyl alcohol resin in carbitol, adding polyether defoamer GP-330, hydrogenated castor oil and amino clay, heating in water bath at 60 ℃, stirring until the polyvinyl alcohol resin is completely dissolved, and sieving with a screen to remove impurities to obtain an organic carrier; the organic carrier comprises the following components in percentage by mass: organic binder: solvent: defoaming agent: thixotropic agent: dispersant = 5:38.5:1.5:1:1, a step of;
(2) Uniformly mixing spherical copper powder and flake copper powder according to the mass ratio of 1:0.4, wherein the average particle size of the spherical copper powder is 0.1-0.5 mu m, the average particle size of the flake copper powder is 2-10 mu m, the average thickness of the flake copper powder is 0.05-0.2 mu m, uniformly dispersing the flake copper powder and capsaicin and diethylene glycol ether acetate by ultrasonic waves, mixing the flake copper powder and the capsaicin and diethylene glycol ether acetate with an organic carrier, and dispersing the mixture to obtain uniform first slurry; fully stirring and dispersing the first slurry in a high-speed mixer for 30min, then performing rolling and dispersing in a three-roller mill for 5 times, wherein the rolling speed is 400rpm, the rolling time is 4h, the rolling fineness is ensured to be less than 1 mu m, the second slurry is obtained, and finally, the second slurry is filtered by a filter screen with the thickness of 10 mu m, so that the environment-friendly antioxidant conductive copper slurry is obtained;
wherein, the environment-friendly antioxidant conductive copper paste ensures that the addition of each component is as follows by mass percent: 45wt.% of copper powder, 5wt.% of organic binder, 8wt.% of bioreductive agent, 3.5wt.% of other additives and 38.5wt.% of solvent.
And after the environment-friendly antioxidant conductive copper paste product is stored for 45 days in the room temperature air atmosphere, the volume resistivity of the copper film obtained after sintering is taken as the average value of three groups of parallel samples to be 4.5 multiplied by 10 -5 Ω·cm。
Example 2
The preparation method of the environment-friendly antioxidant conductive copper paste specifically comprises the following steps:
(1) Dissolving polyvinylpyrrolidone K-30 in butyl carbitol, adding polyether defoamer PPG-1000, polyamide wax and attapulgite clay, heating in water bath at 55 ℃, stirring until the mixture is completely dissolved, and sieving with a screen to remove impurities to obtain an organic carrier; the organic carrier comprises the following components in percentage by mass: organic binder: solvent: defoaming agent: thixotropic agent: dispersant = 7:25:2:2:1, a step of;
(2) The spherical copper powder and the dendritic copper powder are mixed according to the mass ratio of 1:0.5, the average particle size of the spherical copper powder is 0.1-0.5 mu m, the average particle size of the dendritic copper powder is 3-5 mu m, and capsaicin: resveratrol=1:1 (mass ratio) and butyl carbitol solvent are uniformly dispersed by ultrasonic, and then are mixed with an organic carrier and dispersed to obtain uniform first slurry; fully stirring and dispersing the first slurry in a planetary stirrer for 25min, then carrying out rolling and dispersing in a three-roller mill for 5 times, wherein the rolling speed is 500rpm, the rolling time is 3.5h, the rolling fineness is ensured to be less than 1 mu m, a second slurry is obtained, and finally, the second slurry is filtered by a filter screen with the granularity of 8 mu m, so that the environment-friendly antioxidant conductive copper slurry is obtained;
wherein, the environment-friendly antioxidant conductive copper paste ensures that the addition of each component is as follows by mass percent: 53wt.% of copper powder, 7wt.% of organic binder, 10wt.% of bioreductive agent, 5wt.% of other additives and 25wt.% of solvent.
And after the environment-friendly antioxidant conductive copper paste product is stored for 45 days in the room temperature air atmosphere, the volume resistivity of the copper film obtained after sintering is taken as the average value of three groups of parallel samples to be 4.1 multiplied by 10 -5 Ω·cm。
Example 3
The preparation method of the environment-friendly antioxidant conductive copper paste specifically comprises the following steps:
(1) Dissolving acrylic resin in ethylene glycol monoethyl ether, adding an organosilicon defoamer FAG-470, oxidized polyethylene wax and amino clay, heating in a water bath at 45 ℃, stirring until the components are completely dissolved, and sieving with a screen to remove impurities to obtain an organic carrier; the organic carrier comprises the following components in percentage by mass: organic binder: solvent: defoaming agent: thixotropic agent: dispersant = 5:36:2:1.5:0.5;
(2) The spherical copper powder and the rod-shaped copper powder are mixed according to the mass ratio of 1:0.5, and capsaicin: chlorogenic acid=1:1 (mass ratio) and monoethanolamine solvent are uniformly dispersed by ultrasonic, and then mixed with an organic carrier and dispersed to obtain uniform first slurry; fully stirring and dispersing the first slurry in a planetary stirrer for 30min, then carrying out 3 times of rolling and dispersing in a three-roller mill, wherein the rolling speed is 500rpm, the rolling time is 2h, the rolling fineness is ensured to be less than 1 mu m, a second slurry is obtained, and finally, the second slurry is filtered by a 5 mu m filter screen, so that the environment-friendly antioxidant conductive copper slurry is obtained;
wherein, the environment-friendly antioxidant conductive copper paste ensures that the addition of each component is as follows by mass percent: 50wt.% of copper powder, 5wt.% of organic binder, 5wt.% of bioreductive agent, 4wt.% of other additives and 36wt.% of solvent.
And after the environment-friendly antioxidant conductive copper paste product is stored for 45 days in the room temperature air atmosphere, the volume resistivity of the copper film obtained after sintering is taken as the average value of three groups of parallel samples to be 4.8x10 -5 Ω·cm。
Comparative example 1
Comparative example 1 differs from example 1 only in that no bioreductive agent was added, and the other was kept unchanged, and the preparation procedure of comparative example 1 for preparing the environmentally friendly oxidation-resistant conductive copper paste was as follows:
(1) Dissolving polyvinyl alcohol resin in carbitol, adding polyether defoamer GP-330, hydrogenated castor oil and amino clay, heating in water bath at 60 ℃, stirring until the polyvinyl alcohol resin is completely dissolved, and sieving with a screen to remove impurities to obtain an organic carrier; the organic carrier comprises the following components in percentage by mass: organic binder: solvent: defoaming agent: thixotropic agent: dispersant = 5:38.5:1.5:1:1, a step of;
(2) Uniformly mixing spherical copper powder and flake copper powder according to the mass ratio of 1:0.4, wherein the average particle size of the spherical copper powder is 0.1-0.5 mu m, the average particle size of the flake copper powder is 2-10 mu m, the average thickness of the flake copper powder is 0.05-0.2 mu m, uniformly dispersing the flake copper powder and capsaicin and diethylene glycol ether acetate by ultrasonic waves, mixing the flake copper powder and the capsaicin and diethylene glycol ether acetate with an organic carrier, and dispersing the mixture to obtain uniform first slurry; fully stirring and dispersing the first slurry in a high-speed mixer for 30min, then performing rolling and dispersing in a three-roller mill for 5 times, wherein the rolling speed is 400rpm, the rolling time is 4h, the rolling fineness is ensured to be less than 1 mu m, the second slurry is obtained, and finally, the second slurry is filtered by a filter screen with the thickness of 10 mu m, so that the environment-friendly antioxidant conductive copper slurry is obtained;
wherein, the environment-friendly copper paste ensures that the addition of each component is as follows by mass percent: 45wt.% of copper powder, 5wt.% of organic binder, 3.5wt.% of other additives and 38.5wt.% of solvent.
And storing the environment-friendly copper paste product in an air atmosphere at room temperature for 45 days, and sintering to obtain a copper filmVolume resistivity of 7.3X10 -5 The resistivity of the copper film of Ω·cm, which is greater than that of example 1, shows that the environment-friendly oxidation-resistant conductive copper paste added with capsaicin can effectively improve oxidation resistance and thus conductivity, compared with the environment-friendly copper paste without capsaicin.
Comparative example 2
Comparative example 2 differs from example 1 in that the sintering temperature is different, and the preparation of the copper paste of comparative example 1 is carried out according to the formulation described in patent CN109979686a, with the following specific steps:
(1) Adding 45 mass percent of solid high polymer polyester resin into 65 mass percent of diethylene glycol diethyl ether acetate solvent, and obtaining a high polymer polyester resin carrier after dissolving;
(2) And (2) taking silver-coated copper powder with the average particle size of 5-15 mu m, wherein the silver-coated copper powder is flake, adding 45% of silver-coated copper powder by mass percent and 52% of the polymer polyester resin carrier in the step (1) into a high-speed dispersing machine, dispersing by the high-speed dispersing machine to obtain a primary uniform carrier, pouring the carrier into a three-roller machine, grinding and dispersing to obtain a secondary carrier, adding the secondary carrier, 2% of a closed isocyanate curing agent and 1% of a polymer dispersing agent into a planetary mixer, vacuumizing, and removing bubbles to obtain the conductive copper slurry.
After the conductive paste product containing the silver-coated copper powder obtained in the step (2) is stored for 45 days in an air atmosphere at room temperature, sintering and solidification can be realized at 380 ℃, and the volume resistivity of a copper film after sintering is 2.6x10 -5 The composite copper powder with smaller average grain diameter used in the embodiment 1 of the invention greatly reduces the sintering temperature, can realize effective contact between copper powder and copper powder under the condition of reducing the dosage of copper powder, and the biological reducing agent in the invention has effective antioxidation, so that the obtained environment-friendly antioxidation conductive copper paste has strong antioxidation capability, and the obtained copper film product has low resistivity and good conductivity, and besides, the environment-friendly antioxidation conductive copper paste prepared by adopting the technical scheme formula of the invention has better stability and can be stored for a long time for 10 months at room temperature without layering phenomenon.
From the above analysis, compared with comparative examples 1 and 2, the technical scheme of the invention has the advantages of simple process, environment friendliness, high efficiency, good oxidation resistance, low-temperature sintering and curing and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1.一种环保型抗氧化导电铜浆，其特征在于，所述环保型抗氧化导电铜浆的原料按质量百分比计为：铜粉40-70wt.%，有机粘结剂0.1-5wt.%，生物还原剂3-10wt.%，其他添加剂0.1-6wt.%，溶剂10-50wt.%，各原料组分相加的比例为100%；1. An environment-friendly anti-oxidation conductive copper paste is characterized in that the raw materials of the environment-friendly anti-oxidation conductive copper paste are calculated by mass percentage: copper powder 40-70wt.%, organic binder 0.1-5wt.% , bioreductant 3-10wt.%, other additives 0.1-6wt.%, solvent 10-50wt.%, the proportion of each raw material component is 100%; 所述生物还原剂为辣椒素或辣椒素与甲壳素、白藜芦醇、单宁酸、绿原酸、咖啡酸、胡椒碱中的一种或多种组合。The biological reducing agent is one or more combinations of capsaicin or capsaicin and chitin, resveratrol, tannic acid, chlorogenic acid, caffeic acid and piperine. 2.根据权利要求1所述的一种环保型抗氧化导电铜浆，其特征在于，所述其他添加剂包括消泡剂、触变剂和分散剂；其中，2. a kind of environment-friendly anti-oxidation conductive copper paste according to claim 1, is characterized in that, described other additives comprise defoamer, thixotropic agent and dispersant; Wherein, 所述消泡剂为聚醚型消泡剂或有机硅消泡剂，且所述消泡剂占所述环保型抗氧化导电铜浆的质量百分比为0.1-2wt.%；The defoamer is a polyether type defoamer or a silicone defoamer, and the mass percentage of the defoamer to the environmentally friendly anti-oxidation conductive copper paste is 0.1-2wt.%; 所述触变剂为氢化蓖麻油、氧化聚乙烯蜡、聚酰胺蜡、棕榈醇、司盘-85或乙二醇，且所述触变剂占所述环保型抗氧化导电铜浆的质量百分比为0.1-3wt.%；The thixotropic agent is hydrogenated castor oil, oxidized polyethylene wax, polyamide wax, palmityl alcohol, Span-85 or ethylene glycol, and the thixotropic agent accounts for the mass percentage of the environment-friendly anti-oxidation conductive copper paste 0.1-3wt.%; 所述分散剂为氨基粘土或凹凸棒粘土，且所述分散剂占所述环保型抗氧化导电铜浆的质量百分比为0.1-1wt.%；The dispersant is amino clay or attapulgite clay, and the dispersant accounts for 0.1-1wt.% of the mass percentage of the environmentally friendly anti-oxidation conductive copper paste; 且，所述氨基粘土的制备方法如下：And, the preparation method of described amino clay is as follows: 将六水合氯化镁溶于200mL无水乙醇中，充分搅拌30 min，滴加γ-氨丙基三乙氧基硅烷，持续搅拌至反应完全，将得到的白色悬浮液在5000 rpm下离心5 min，然后在真空干燥箱中45℃干燥24h，研磨成粉即得所述氨基粘土，并放入干燥器中待用；Dissolve magnesium chloride hexahydrate in 200 mL of absolute ethanol, stir thoroughly for 30 min, add γ-aminopropyltriethoxysilane dropwise, and continue stirring until the reaction is complete, centrifuge the obtained white suspension at 5000 rpm for 5 min, Then dry it in a vacuum oven at 45°C for 24 hours, grind it into powder to obtain the amino clay, and put it in a desiccator for use; 其中，γ-氨丙基三乙氧基硅烷：六水合氯化镁的物质的量比为1.25-1.35。Wherein, the molar ratio of γ-aminopropyltriethoxysilane:magnesium chloride hexahydrate is 1.25-1.35. 3.根据权利要求2所述的一种环保型抗氧化导电铜浆，其特征在于，所述聚醚型消泡剂为聚醚消泡剂GP-330、聚醚消泡剂GPE-3000或聚醚消泡剂PPG-1000，所述有机硅消泡剂为有机硅消泡剂FAG-470、有机硅消泡剂BYK-065、有机硅消泡剂BYK-066N或聚硅氧烷消泡剂YCK-615。3. A kind of environment-friendly anti-oxidation conductive copper paste according to claim 2, characterized in that, the polyether type defoamer is polyether defoamer GP-330, polyether defoamer GPE-3000 or Polyether defoamer PPG-1000, the silicone defoamer is silicone defoamer FAG-470, silicone defoamer BYK-065, silicone defoamer BYK-066N or polysiloxane defoamer agent YCK-615. 4.根据权利要求1所述的一种环保型抗氧化导电铜浆，其特征在于，所述铜粉至少为球状铜粉、片状铜粉、树枝状铜粉、棒状铜粉、纤维状铜粉、多面体铜粉中的一种，其中，4. A kind of environment-friendly anti-oxidation conductive copper paste according to claim 1, characterized in that, the copper powder is at least spherical copper powder, flake copper powder, dendritic copper powder, rod-shaped copper powder, fibrous copper powder Powder, one of polyhedral copper powder, wherein, 球状铜粉的平均粒径为0.05-0.5µm；片状铜粉的平均粒径为2-10µm、平均厚度为0.05-0.2µm；树枝状铜粉的平均粒径为3-5µm；棒状铜粉的平均直径为0.05-0.1µm、平均长度为1-2.5µm；纤维状铜粉的平均直径为0.03-0.05µm、平均长度为10-30µm；多面体铜粉的平均粒径为0.1-2µm。The average particle size of spherical copper powder is 0.05-0.5µm; the average particle size of flake copper powder is 2-10µm, and the average thickness is 0.05-0.2µm; the average particle size of dendritic copper powder is 3-5µm; rod-shaped copper powder The average diameter of the copper powder is 0.05-0.1µm, and the average length is 1-2.5µm; the average diameter of the fibrous copper powder is 0.03-0.05µm, and the average length is 10-30µm; the average particle size of the polyhedral copper powder is 0.1-2µm. 5.根据权利要求1所述的一种环保型抗氧化导电铜浆，其特征在于，所述有机粘结剂为聚乙烯醇树脂、聚乙烯吡咯烷酮K-30、聚乙二醇-400、丙烯酸树脂、羟乙基纤维素、羟丙基纤维素、明胶、虫胶或阿拉伯树胶。5. A kind of environment-friendly oxidation-resistant conductive copper paste according to claim 1, characterized in that, the organic binder is polyvinyl alcohol resin, polyvinylpyrrolidone K-30, polyethylene glycol-400, acrylic acid Resin, hydroxyethylcellulose, hydroxypropylcellulose, gelatin, shellac or acacia. 6.根据权利要求1所述的一种环保型抗氧化导电铜浆，其特征在于，所述溶剂至少为松油醇、卡必醇、丁基卡必醇、二甘醇醚醋酸酯、邻苯二甲酸二丁酯、柠檬酸三丁酯、乙二醇、丙二醇、氨甲基丙醇、二甘醇、三甘醇、二甘醇甲醚、乙二醇单甲醚、乙二醇单乙醚、单乙醇胺、二乙醇胺、三乙醇胺中的一种。6. a kind of environment-friendly anti-oxidation conductive copper paste according to claim 1, is characterized in that, described solvent is at least terpineol, carbitol, butyl carbitol, diethylene glycol ether acetate, ortho Dibutyl phthalate, tributyl citrate, ethylene glycol, propylene glycol, aminomethylpropanol, diethylene glycol, triethylene glycol, diethylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol mono One of ether, monoethanolamine, diethanolamine, triethanolamine. 7.一种如权利要求1~6任一所述环保型抗氧化导电铜浆的制备方法，其特征在于，包括如下步骤：7. A preparation method of an environment-friendly anti-oxidation conductive copper paste according to any one of claims 1 to 6, characterized in that, comprising the steps: （1）将有机粘结剂溶解于溶剂中，加入消泡剂、触变剂和分散剂，水浴加热温度为30-60℃，搅拌至完全溶解，用300目的不锈钢网或聚酯网过滤除杂，得到有机载体；所述有机载体中各组分添加量按质量比为：有机粘结剂：溶剂：消泡剂：触变剂：分散剂=0.1-8：10-50：0.1-2：0.1-3：0.1-1；(1) Dissolve the organic binder in the solvent, add defoamer, thixotropic agent and dispersant, heat the water bath at 30-60°C, stir until it is completely dissolved, and filter it out with 300-mesh stainless steel mesh or polyester mesh Miscellaneous, to obtain an organic vehicle; the addition amount of each component in the organic vehicle is according to the mass ratio: organic binder: solvent: defoamer: thixotropic agent: dispersant = 0.1-8: 10-50: 0.1-2 :0.1-3:0.1-1; （2）将铜粉、生物还原剂及所述溶剂超声分散均匀，再与所述有机载体混合并进行分散，得到均匀的第一浆料；控制第一浆料的粘度为15Pa·s-65Pa·s，并将第一浆料于高速混料机或行星搅拌机中充分搅拌分散10-30min，接着在三辊轧机中进行3-5次辊轧分散，辊轧转速为400-500rpm，辊轧时间为2-5h，保证辊轧细度小于1µm，得到第二浆料，最终经5-10µm的滤网过滤，得到所述环保型抗氧化导电铜浆。(2) Ultrasonic disperse the copper powder, biological reducing agent and the solvent, and then mix and disperse with the organic carrier to obtain a uniform first slurry; control the viscosity of the first slurry to 15Pa·s-65Pa s, and fully stir and disperse the first slurry in a high-speed mixer or a planetary mixer for 10-30 minutes, then carry out rolling and dispersing in a three-roll mill for 3-5 times, the rolling speed is 400-500rpm, rolling The time is 2-5 hours, and the rolling fineness is guaranteed to be less than 1 µm to obtain the second slurry, which is finally filtered through a filter screen of 5-10 µm to obtain the environment-friendly anti-oxidation conductive copper paste. 8.根据权利要求7所述的一种环保型抗氧化导电铜浆的制备方法，其特征在于，所述环保型抗氧化导电铜浆可在180-200℃实现低温固化，且所述环保型抗氧化导电铜浆产品在室温空气氛围中存放45天后，烧结后铜线或铜膜的体积电阻率仍小于5×10-5Ω·cm。8. The preparation method of a kind of environment-friendly anti-oxidation conductive copper paste according to claim 7, characterized in that, the environment-friendly anti-oxidation conductive copper paste can be cured at a low temperature of 180-200°C, and the environment-friendly type After the anti-oxidation conductive copper paste product is stored in the air atmosphere at room temperature for 45 days, the volume resistivity of the sintered copper wire or copper film is still less than 5×10 -5 Ω·cm. 9.一种如权利要求1~6任一项所述环保型抗氧化导电铜浆或如权利要求7所述方法制备的环保型抗氧化导电铜浆在柔性器件中的应用。9. An application of an environment-friendly anti-oxidation conductive copper paste according to any one of claims 1 to 6 or an environment-friendly anti-oxidation conductive copper paste prepared by the method according to claim 7 in flexible devices.
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